EP1490216B1 - Procede de fabrication d'elements composites - Google Patents

Procede de fabrication d'elements composites Download PDF

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Publication number
EP1490216B1
EP1490216B1 EP03720337A EP03720337A EP1490216B1 EP 1490216 B1 EP1490216 B1 EP 1490216B1 EP 03720337 A EP03720337 A EP 03720337A EP 03720337 A EP03720337 A EP 03720337A EP 1490216 B1 EP1490216 B1 EP 1490216B1
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EP
European Patent Office
Prior art keywords
iii
hollow bodies
space
filled
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP03720337A
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German (de)
English (en)
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EP1490216A1 (fr
Inventor
Thomas DRÖGE
Jürgen Mertes
Edmund Stadler
Georg Knoblauch
Stefanie LÜNNE
Jürgen BOOS
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BASF SE
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BASF SE
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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/296—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and non-metallic or unspecified sheet-material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
    • B32B3/18—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side
    • B32B3/20—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by an internal layer formed of separate pieces of material which are juxtaposed side-by-side of hollow pieces, e.g. tubes; of pieces with channels or cavities
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/26—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups
    • E04C2/284—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating
    • E04C2/292—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials composed of materials covered by two or more of groups E04C2/04, E04C2/08, E04C2/10 or of materials covered by one of these groups with a material not specified in one of the groups at least one of the materials being insulating composed of insulating material and sheet metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]

Definitions

  • the invention relates to ships or structures containing the composite elements produced by the process according to the invention.
  • the length data shown for the layers (i), (ii) and (iii) relate to the thicknesses of the respective layers.
  • hulls of tankers usually consist of an inner and an outer hull, each hull being constructed of 15 mm thick steel plates connected by 2 m long steel struts. Since these steel plates are exposed to considerable forces, both the outer and the inner steel shell are stiffened by welded reinforcing elements. Disadvantages of these classic construction parts are the considerable amounts of steel required as well as the time-consuming and labor-intensive production.
  • SPS elements Sandwich Plate System
  • PLC elements include a composite of metal and plastic.
  • the adhesion of the plastic to the two metal layers produces composite elements with extraordinary advantages over known steel constructions.
  • PLC elements are known from the documents US Pat. No. 6,050,208 . US 5,778,813 .
  • DE-A 198 25 083 DE-A 198 25 085 .
  • DE-A 198 25 084 DE-A 198 25 087 and DE-A 198 35 727 ,
  • the hollow bodies preferably have a density of less than 1 g / cm 3 , more preferably 0.1 to 0.6 g / cm 3 .
  • the density is the "true particle density", ie the quotient of the weight of the hollow body and the volume of the hollow body when the hollow body is completely surrounded by gas.
  • the hollow bodies preferably hollow spheres, preferably have an average wall thickness of 5 to 20% of the hollow body diameter.
  • the hollow bodies may be based on generally known materials, for example plastics, for example polyethylene, polypropylene, polyurethane, polystyrene or a mixture thereof, or mineral materials, eg clay, aluminum silicate, glass, but preferably glass, aluminum silicate or ceramic, more preferably glass.
  • the hollow body 1 to 60%, more preferably 10 to 40% of the total volume, ie including the hollow body, the layer (ii).
  • the hollow body may have in its cavity walls or other structural elements.
  • the cavity of the hollow body can be filled, for example, with air, inert gases, for example nitrogen, helium or argon, or reactive gases, for example oxygen or other known gases, preferably with air, and completely or predominantly, preferably completely, from the material of the hollow body described at the beginning be enclosed.
  • the shape of the hollow bodies may be spherical or irregular.
  • the hollow bodies may have a vacuum or partial vacuum in the cavity. Preference is given to using hollow glass microspheres as the hollow body.
  • the hollow glass microspheres have a compressive strength of at least 15 bar.
  • the layer (ii) is preferably polyisocyanate polyaddition products obtainable by reacting the starting materials (a) isocyanate and (b) isocyanate-reactive compounds.
  • the preparation of the composite elements according to the invention can thus preferably be carried out in such a way that for the preparation of (ii) (a) isocyanates and (b) isocyanate-reactive compounds in Gegenart of hollow bodies having an outer diameter less than 500 microns.
  • the hollow bodies may be added to component (b) and / or component (a) and / or liquid reaction products of (a) and (b).
  • the addition can take place directly in the mixing head, for example the pump, or else already in the reservoir of the starting components (a) and / or (b).
  • the mixing of the hollow body can be done both by hand, for example by means of a hand mixer, or by means of known stirrer.
  • High- and low-pressure machines can be used, wherein the mixing head is preferably to be modified so that the hollow bodies do not break during processing when the shearing forces occur.
  • a component can be filled simultaneously via 2 or more mixing heads or machines.
  • a mixing device for mixing the hollow body according to the invention with (a) and / or (b) and / or reaction products of (a) and (b) is, for example, a preferably continuously operating device constructed from a mixing pot, a feed line for (a), (b) and / or a liquid reaction product of (a) with (b), a feed line for hollow microspheres, a stirrer and a controllable outlet opening suitable.
  • This preferred mixing device can be upstream or downstream of the high and / or low-pressure machine with the mixing head (s), preferably upstream or also part of these machines.
  • the mixing pot As a mixing pot conventional reaction vessels, such as steel, glass or plastic, such as epoxy resin serve.
  • the mixing pot is constructed funnel-shaped, wherein the outlet opening is located at the funnel neck.
  • this funnel is arranged vertically.
  • the size of the mixing pot depends on the scale in which the process according to the invention is to be carried out; in general, the mixing pot can be of microscale, ie for example comprising a volume of a few cm 3 , up to the macroscale, ie comprising a volume of up to a few m 3 , operate.
  • the inlets lead to the mixing pot.
  • the amounts of feed are separately controllable.
  • the metering of the feedstock to reactive raw materials for the preparation of (ii) can be carried out, for example, by a known PUR metering device, the metering of the feed to hollow microspheres can be effected, for example, by a screw metering device.
  • the mixing device is preferably equipped with a stirring element.
  • this agitator ensures mixing and, on the other hand, a constant transport of the mixture within the mixing pot from the inlets to the outlet.
  • conventional stirrers such as disc stirrers or paddle stirrers, are generally suitable. It is preferred that the stirrer is adjusted so that the stirring is free of dead space. Different stirrer sizes and geometries allow for optimal adaptation to the mixing requirements required for different viscosities and throughputs.
  • the stirring member is adjusted and operated at a speed so that as possible no damage to the hollow microspheres occurs.
  • the proportion of damaged hollow glass microspheres after incorporation is generally less than 40% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, particularly preferably less than 2% by weight and in particular less than 1% by weight .%, Based on the total weight of the used hollow glass microspheres. The proportion may optionally vary depending on the density of the hollow spheres used.
  • the exit of the starting material containing the hollow body according to the invention for the production of (ii) takes place at the outlet opening.
  • the outlet opening is preferably adjustable.
  • control is effected by a conical closure, which can be moved in the vertical direction to the outlet opening. By completely lowering the cone, the outlet opening can be completely closed, by wide lifting it can be fully opened. In this way a dosage of the leaking product is possible.
  • this conical closure is integrated on the stirring element.
  • other control devices that provide the desired control effect are also possible.
  • the average residence time can be controlled in the mixing device. In general, this is between 0.1 and 10 minutes, preferably between 0.1 and 1 minutes.
  • the reaction and the mixing so that the mixture emerging directly at the outlet opening has a viscosity of 1000 to 30,000 mPas, wherein the viscosity at room temperature (25 ° C) determined using a cone-plate rotation viscometer geometry becomes.
  • a parameter for an optimal residence time in the mixing pot can also serve the permanent detection of the outlet temperature.
  • An outlet temperature of 20 ° C to 100 ° C, preferably 20 ° C to 80 ° C, more preferably 20 ° C to 50 ° C, ensures a sufficient "open time” (until the material is solid) and prevents excessive exothermic Reaction, which would result in a "solidification" of the polyurethane already in the mixing pot and thus would entail the discontinuation of the manufacturing process.
  • the control of the process is feasible in this way without considerable technical effort for the skilled person.
  • the starting materials for the preparation of (ii) are preferably filled in the liquid state in the space between (i) and (iii), preferably during this filling process, a negative pressure in the space to be filled between (i) and (iii) is generated.
  • a negative pressure in the space to be filled is generated.
  • the negative pressure in the space to be filled is 0.2 bar to 0.8 bar, ie the pressure in the mold to be filled is 0.8 to 0.2 bar lower than the ambient air pressure.
  • the negative pressure that can be generated, for example, by well-known vacuum pumps, is preferably achieved in that (i) and / or (iii) in addition to the orifices (iv) in (i) and / or (iii), via the the starting materials for the preparation of (ii) are introduced, have at least one further opening (v) over which the negative pressure is applied.
  • a hose is interposed between a vacuum pump which generates the negative pressure and the opening (v) in (i). This hose can for example be pressed or glued to (i).
  • the amounts of starting materials for the preparation of (ii) are difficult to be such that just the space to be filled (R) is filled, but overflow is prevented.
  • a larger amount of starting components for the preparation of (ii) is preferably added to the space between (i) and (iii) than it can take up.
  • the resulting overflow is preferably removed via openings (v).
  • openings (v) As soon as the space between (i) and (iii) is completely filled with the starting components for the preparation of (ii), filling can be stopped by opening the liquid in the tube, which is preferably transparent, and opening (iv) and (v ) are closed.
  • the closing of the openings can be carried out, for example, with a plastic or metal plug, preferably with a screw cap which is located either in the overflow vessel or preferably between the overflow vessel and (i) and / or (iii).
  • the openings (iv) remain preferably until the end of the curing process of the mixture (a) and (b) closed by the fixed mixing head.
  • the space to be filled between (i) and (iii) only the openings (iv) and (v), wherein at (iv) the outflow end, preferably mixing head is and (v) the negative pressure is applied. Since according to this preferred embodiment, no air can get into the space to be filled, it is possible to generate a negative pressure.
  • the layers (i) and (iii) have no features that can be used to attach a discharge end to fill the space between (i) and (iii) with liquids.
  • the term "outflowing" may be conventional means by which liquids are filled, such as filler neck, hose ends, mixing heads, static mixers or the like.
  • the outflow end is a mixing head.
  • mixing heads are well known and commercially available, for example, in connection with conventional metering devices for polyurethane systems.
  • the attachment of the outflow end, preferably of the mixing head, may preferably take place such that the outflow end of the conveyor or a holder for the outflow end of the conveyor screwed to the layer (i) at at least three locations, preferably three to six locations, more preferably four or five locations becomes.
  • the liquid is filled through at least one opening (iv) in (i) and / or (iii) in the space between (i) and (iii).
  • a mixing head for example, bolts with a thread, which serve for fastening the mixing head or a holder for the mixing head, can shoot into the layer (i).
  • the bolts can preferably taper at the side facing away from the thread in order to make it easier to introduce them into the layer (i).
  • the bolts preferably have a diameter of 6 mm to 20 mm and a length of 8 mm to 42 mm.
  • the thread that is directed outwards after the fixation of the bolts, i. on the side of (i), which faces away from (iii), preferably has a length of 4 mm to 30 mm.
  • the insertion of the bolts is carried out, for example, by firing with a bolt pusher, which is commercially available e.g. available from Hilti.
  • (i) has threads with which the outflow end at the opening (iv), through which the liquid is filled, is screwed to (i).
  • an O-ring made of an elastic material.
  • O-rings are well known and can be matched in their dimensions to the diameter of the opening (iv) and the mixing head.
  • the mixing head is thus fixed close to the opening (iv) in (i) or (iii), through which the entry of the starting materials takes place.
  • the outflow end is not fastened directly to the layer (i), but rather it fixes the outflow end to a holder which is screwed to (i).
  • this bracket made of common materials, such as plastics. Wood or preferably conventional metals may be, it is preferably a construction, which has holes through which the (i) fixed threads are guided and fastened for example by means of appropriate nuts.
  • the holder has fastening elements for the outflow end, for example plug connections, screw connections or edges with which the outflow end can be clamped by elastic bands to the holder.
  • the outflow end is fastened to the holder at at least three points in order to avoid tilting. It is thus preferable to screw a holder to at least three threads which are fastened to (i) and fix the mixing head to this holder.
  • the bolts can be sawed off, for example, on the surface of (i) after completion of the composite elements.
  • the filling of the space between (i) and (iii) can be carried out with conventional conveyors, preferably continuously, for example with high and low pressure machines, preferably low pressure machines.
  • the filling preferably takes place with a low-pressure machine (for example from Cannon) via one or more, preferably a mixing head, in which the starting components are mixed, in a single working step, preferably an injection process.
  • a single injection operation means that the filling of the space between (i) and (iii), for example, with the starting materials for the production of (ii) is not interrupted before the complete filling.
  • the starting materials are thus preferably given in a single shot under pressure in the space between (i) and (iii).
  • the liquid is a reactive mixture that cures with the reaction.
  • the filling of the space between (i) and (iii) can take place both in the vertical orientation of (i) and (iii), as well as in the horizontal orientation of (i) and (iii).
  • the layers (i) and (iii) may preferably be used as conventional plastic, wood or preferably metal plates, for example iron, steel, copper and / or aluminum plates, with the thicknesses according to the invention.
  • Both (i) and (ii) can be coated, for example primed, primed, painted and / or coated with conventional plastics, used in the production of the composite elements according to the invention. Preference is given to using (i) and (iii) uncoated and particularly preferably purified, for example, by customary sandblasting.
  • This offers the advantage that in particular to be filled liquid components which are reactive towards water, for example isocyanates, do not react in undesired side reaction.
  • the drying which preferably takes place directly before filling, can be effected, for example, by means of hot air or by means of compressed air.
  • the space to be filled between (i) and (iii) can be dried by a blower, the air through openings (iv) and (v) in (i) and / or (iii) through the space to be filled between (i) and (iii) directs.
  • the openings (iv) and (v) are preferably bores in (i) and / or (iii) with a diameter of 0.5 to 5.0 cm in (i) and / or (iii).
  • the space filled between (i) and (iii) with the starting materials to produce (ii) need not represent the entire space between (i) and (iii). Both (i) and (iii) may survive at the edges over (ii), i. only in a subset of (i) and (iii) does one bind (i) over (ii) to (iii).
  • the space between (i) and (iii) may be sealed prior to being filled with the source materials such that the seal is within the space enclosed by (i) and (iii) and edges of (i) and / or (iii ) survive.
  • the delivery rate can be varied depending on the volume to be filled.
  • the delivery rate and delivery device are preferably selected such that the space to be filled can be filled within 0.5 to 20 minutes with the components for the production of (ii).
  • the layers (i) and (iii) are fixed in a suitable arrangement, for example parallel to one another.
  • the distance is usually chosen so that the space (R) between (i) and (iii) has a thickness of 10 to 300 mm.
  • the fixation of (i) and (iii) can be done, for example, by spacers, for example in a mold or suitable holder.
  • the edges of the gap are usually sealed in such a way that the space between (i) and (iii) can be completely filled with the liquid or the starting components for the production of (ii), however, a flow-out of these starting components before complete filling is prevented .
  • the sealing can be done with conventional plastic, paper or metal foils and / or plates, which are glued, for example, welded or pressed and which can optionally also serve as spacers. This preferred sealing does not relate to the preferred apertures (iv) and (v), which have been presented initially.
  • the check of the tightness of (R) before filling with the starting components is preferably carried out by pressure difference measurement.
  • pressure differential measurement is understood to mean that one tries to build a pressure difference between the space (R) and the external environment over a certain period of time, for example by trying to (A) under or over pressure in relation to the external environment to reach. This can be achieved by conventional vacuum pumps or well-known compressors that pump air or gas into the room (R). If a stable overpressure or underpressure can be generated in (R), this indicates a sufficiently dense cavity that can be filled with the starting components to produce (ii).
  • the openings (iv) or (v), which are provided for filling (R) with the starting components or as vents or as overflow openings for the discharge of excess output components, also temporarily seals. If appropriate, at least one of these openings can serve to connect the vacuum pump or compressor to (R).
  • the mold to be filled preferably consists of the specified layers (i) and (iii) and (vi), which are preferably arranged in parallel, and preferably seals between the layers (i) and (iii), which run out of liquid during filling prevent.
  • the layer (ii) is thus preferably adhesively disposed between the layers (i) and (iii).
  • the composite elements according to the invention can preferably be produced in such a way that a planar structure (vi) is substantially parallel, preferably parallel, at a distance of 5 mm to 150 mm, preferably 15 mm to 50 mm, particularly preferably 15 mm to 30 mm the layer (i) fixed, the layer (iii) fixed substantially parallel to (i) and (vi), the space to be filled with (ii) except for openings, for example, the openings described in this document (iv) and (v ), which are required for filling, seals and then fills the space to be filled with the starting materials to produce (ii).
  • fixation of (vi) with (i) can, for example, be carried out in the case of horizontal alignment of (i) in such a way that spacers, For example, wood, plastic or metal blocks with a suitable height on the layer (i) brings and on these spacers the structure (vi) sets.
  • spacers For example, wood, plastic or metal blocks with a suitable height on the layer (i) brings and on these spacers the structure (vi) sets.
  • the layer (iii) can be fixed at a suitable distance, ie at a suitable layer thickness of (ii), preferably parallel to (i) and (vi), for example by taking metal plates at the edges of the space to be occupied by (ii) fixed to (i), for example, welds, preferably perpendicular to (i), and on these metal plates, which bound and terminate the lateral edge of (ii), the layer (iii) fixed, for example, welded.
  • the starting materials are preferably continuously introduced without interruption in a single step in the space to be filled between (i) and (iii), more preferably one will enter the starting materials by means of a high pressure apparatus via one or more mixing heads, for example, fill.
  • the liquid for the preparation of (ii) (a) isocyanates and (b) isocyanate-reactive compounds.
  • the layer (ii) thus preferably represents polyisocyanate polyaddition products.
  • starting materials or “starting components” are in particular (a) isocyanates and (b) isocyanate-reactive compounds, but if appropriate, as far as they are used (c) gases, (d) catalysts, (e) auxiliaries and / or (f) propellants.
  • the starting components for the preparation of the polyisocyanate polyaddition products are usually mixed at a temperature of 0 to 100 ° C, preferably from 20 to 60 ° C, and introduced as already described in the space between (i) and (iii).
  • the mixing can be done mechanically by means of a stirrer or a stirring screw.
  • the reaction temperature, i. the temperature at which reaction takes place is usually> 20 ° C., preferably 50 to 150 ° C., depending on the material thickness.
  • the layer (ii) of the composite elements according to the invention preferably has a modulus of elasticity of> 275 MPa in the temperature range of -45 to +50 ° C (according to DIN 53457), an adhesion to (i) and (iii) of> 4 MPa (according to DIN 53530), an elongation of> 30% in the temperature range from -45 to +50 ° C (according to DIN 53504), a tensile strength of> 20 MPa (according to DIN 53504) and a compressive strength of> 20 MPa (according to DIN 53421).
  • the density of the layer (ii), ie including the hollow body according to the invention is preferably 350 kg / m 3 to 1200 kg / m 3 , particularly preferably 650 kg / m 3 to 1000 kg / m 3 .
  • the preparation of the composite elements according to the invention can be carried out such that between (i) and (iii) polyisocyanate polyaddition products (ii), usually polyurethanes, which may optionally have urea and / or isocyanurate structures, by reacting (a) isocyanates with ( b) compounds which are reactive towards isocyanates, if appropriate in the presence of blowing agents (f), 1 to 50 % By volume, based on the volume of the polyisocyanate polyaddition products, of at least one gas (c), (d) catalysts and / or (e) auxiliaries, preferably (ii) adhering to (i) and (iii).
  • polyisocyanate polyaddition products (ii) has been described many times.
  • the surfaces of (i) and (iii) may preferably be blasted with corundum or iron gravel prior to making the composite elements for cleaning and increasing the surface roughness with sand or steel balls.
  • This blasting can be carried out by the usual methods in which the blasting material impinges, for example, under high pressure on the surfaces. Suitable apparatus for such treatment are commercially available.
  • This treatment of the surfaces of (i) and (iii) which are in contact with (ii) after the reaction of (a) with (b) leads to a significantly improved adhesion of (ii) to (i) and (iii ).
  • the blasting is preferably carried out immediately before the introduction of the components for the preparation of (ii) in the space between (i) and (iii).
  • the surfaces of (i) and (iii) to which (ii) is to adhere are preferably free of inorganic and / or organic substances which reduce adhesion, for example dust, dirt, oils and fats or substances generally known as mold release agents.
  • Suitable isocyanates (a) are the aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates known per se, preferably diisocyanates, which may optionally have been biuretized and / or isocyanurated by generally known processes.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical such as 1,12-dodecane diisocyanate, 2-ethyl-tetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, lysine-ester-diisocyanate (LDI) , Hexamethylene diisocyanate-1,6 (HDI), cyclohexane-1,3- and / or 1,4-diisocyanate, 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2 ' and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, 1-isocyanato-3,3,5-trimethyl-5-isocyanato
  • di- and / or polyisocyanates containing ester, urea, allophanate, carbodiimide, uretdione and / or urethane groups can be used in the process according to the invention.
  • isocyanate-reactive compounds there can be used, for example, compounds having as isocyanate-reactive groups hydroxyl, thiol and / or primary and / or secondary amino groups and usually having a molecular weight of 60 to 10,000 g / mol, e.g. Polyols selected from the group of polymer polyols, polyether polyols, polyester polyols, polythioether polyols, hydroxyl-containing polyacetals and hydroxyl-containing aliphatic polycarbonates or mixtures of at least two of said polyols. These compounds usually have a functionality towards isocyanates of from 2 to 6 and a molecular weight of from 400 to 8000 and are generally known to the person skilled in the art.
  • suitable polyether polyalcohols which according to known technology by addition of alkylene oxides, for example tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and / or 1,2-propylene oxide of conventional Starter substances are available.
  • alkylene oxides for example tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and / or 1,2-propylene oxide of conventional Starter substances.
  • starter substances it is possible to use, for example, known aliphatic, araliphatic, cycloaliphatic and / or aromatic compounds which contain at least one, preferably 2 to 4, hydroxyl groups and / or at least one, preferably 2 to 4, amino groups.
  • ethanediol diethylene glycol, 1,2- or 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, glycerol, trimethylolpropane, neopentyl glycol, Sugars, for example sucrose, pentaerythritol, sorbitol, ethylenediamine, propanediamine, neopentanediamine, hexamethylenediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2- (ethylamino) ethylamine, 3- (methylamino) propylamine, diethylenetriamine, dipropylenetriamine and / or N, N ' Bis (3-aminopropyl) ethylenediamine can be used.
  • sucrose pentaerythr
  • alkylene oxides can be used individually, alternately in succession or as mixtures.
  • alkylene oxides are used which lead to primary hydroxyl groups in the polyol.
  • Particularly preferred polyols used are those which have been alkoxylated with ethylene oxide to complete the alkoxylation and thus have primary hydroxyl groups.
  • polyether polyols As polymer polyols, a special class of polyether polyols, it is possible to use compounds known in general from polyurethane chemistry, preferably styrene-acrylonitrile graft polyols.
  • polymer polyols can significantly reduce the shrinkage of the polyisocyanate polyaddition product, for example of the polyurethane and thus lead to improved adhesion of (ii) to (i) and (iii).
  • propellant (f) may be preferred. and / or gases (c) are used.
  • Suitable polyester polyols can be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • the polyester polyols preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 480 to 3000, preferably 600 to 2000 and in particular 600 to 1500.
  • the composite elements according to the invention are preferably prepared using polyether polyalcohols as component (b) for reaction with the isocyanates, advantageously those having an average functionality towards isocyanates of 1.5 to 8, preferably 2 to 6, and a molecular weight of 400 to 8000.
  • polyether polyalcohols offer significant advantages through improved stability of the polyisocyanate polyaddition products to hydrolytic cleavage and lower viscosity, as compared to polyester polyalcohols, respectively.
  • the improved stability against hydrolysis is particularly advantageous when used in shipbuilding.
  • the lower viscosity of the polyether polyhydric alcohols and the reaction mixture for preparing (ii) containing the polyether polyalcohol allows a faster and easier filling of the space between (i) and (iii) with the reaction mixture for producing the composite elements. Due to the considerable dimensions, in particular of structural parts in shipbuilding, low-viscosity liquids are of considerable advantage.
  • isocyanate-reactive compounds in addition to the above-mentioned compounds having a usual molecular weight of 400 to 8,000, diols and / or triols having molecular weights of 60 to ⁇ 400 may be used as a chain extender and / or crosslinking agent in the process of the present invention.
  • chain extenders, crosslinking agents or, if appropriate, mixtures thereof can prove to be advantageous for modifying the mechanical properties, for example the hardness.
  • the chain extenders and / or crosslinkers preferably have a molecular weight of 60 to 300.
  • Suitable examples include aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, decane-1,10, o-, m-, p-dihydroxycyclohexane, diethylene glycol , Dipropylene glycol and preferably 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols such as 1,2,4-, 1,3,5-trihydroxycyclohexane, glycerol and Trimethylolpropane, low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1,2-propylene oxide and the aforementioned diols and / or triols as starter molecules and / or diamines such as diethyltoluenediamine and / or 3,5-di
  • chain extenders, crosslinking agents or mixtures thereof are used for preparing the polyisocyanate polyaddition products, these are expediently used in an amount of from 0 to 30% by weight, preferably from 1 to 30% by weight, based on the weight of the total isocyanate used reactive compounds (b) are used.
  • carboxylic acids can be used to optimize the curing process in the preparation of (ii).
  • carboxylic acids are formic acid, acetic acid, succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, citric acid, benzoic acid, salicylic acid, phenylacetic acid, phthalic acid, toluenesulfonic acid, derivatives of said acids, isomers of said acids and any mixtures of said acids.
  • the proportion by weight of these acids may be from 0 to 5% by weight, preferably from 0.2 to 2% by weight, based on the total weight of (b).
  • the use of amine-initiated polyether polyalcohols can improve the curing behavior of the reaction mixture to produce (ii).
  • the compounds (b), as well as the other components for the preparation of (ii) are used with the lowest possible content of water in order to avoid the formation of carbon dioxide by reaction of the water with isocyanate groups.
  • component (c) for the preparation of (ii) it is possible to use generally known compounds which have a boiling point at a pressure of 1 bar of less (ie lower than) -50 ° C., for example air, carbon dioxide, nitrogen, helium and / or neon. Preferably, air is used.
  • the component (c) is preferably inert to the component (a), more preferably to the components (a) and (b), i.e. to be inert. a reactivity of the gas towards (a) and (b) is hardly, preferably not detectable.
  • the use of gas (c) is fundamentally different from the use of conventional blowing agents to produce foamed polyurethanes.
  • component (c) is preferably already used in gaseous form as an aerosol, for example in the polyol component.
  • catalysts (d) it is possible to use generally known compounds which are the reaction of isocyanates with the isocyanate-reactive compounds greatly accelerating, wherein preferably a total catalyst content of 0.001 to 15 wt .-%, in particular 0.05 to 6 wt .-%, based on the weight of the total isocyanate-reactive compounds used.
  • the following compounds can be used: triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-diamino-diethyl ether, bis (dimethylaminopropyl) -urea, N-methyl- or N-ethylmorpholine , N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiperazine, N Dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo- (2,2,0) -octane, 1,4-diazabicyclo
  • dimethylaminopropyl) -s-hexahydrotriazine ferrous chloride, zinc chloride, lead octoate and preferably tin salts such as tin dioctoate, tin diethylhexoate, dibutyltin dilaurate and / or dibutyldilaurylzine mercaptide, 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, alkali metal hydroxides, such as sodium hydroxide, alkali metal alkoxides, such as sodium methylate and potassium isopropylate, and / or alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and optionally pendant OH groups.
  • tin salts such as tin dioctoate, tin diethylhexoate, dibutyl
  • adjuvants may be included in the reaction mixture for the preparation of the polyisocyanate polyadducts (ii).
  • examples which may be mentioned include fillers, surface-active substances, dyes, pigments, flame retardants, hydrolysis protectants, fungistatic, bacteriostatic substances and foam stabilizers.
  • Suitable surface-active substances are, for example, compounds which serve to assist the homogenization of the starting materials and, if appropriate, are also suitable for regulating the structure of the plastics. Mention may be made, for example, of emulsifiers, such as the sodium salts of castor oil or of fatty acids and salts of fatty acids with amines, for example diethylamine, diethanolamine stearate, ricinoleic diethanolamine, salts of sulfonic acids, for example alkali metal or ammonium salts of dodecylbenzene- or dinaphthylmethanedisulfonic acid and ricinoleic acid.
  • the surface-active substances are usually used in amounts of from 0.01 to 5% by weight, based on 100% by weight, of the total isocyanate-reactive compounds (b) used.
  • Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tetrakis (2) chloroethyl) ethylenediphosphate, dimethylmethanephosphonate, Diethanolaminomethylphosphonklarediethylester and commercially available halogen-containing flame retardant.
  • Fillers which may optionally be used in addition to the hollow bodies according to the invention are, for example, the customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating compositions, etc.
  • inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, and glass, etc.
  • kaolin China Clay
  • aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal and glass fibers of short length.
  • Suitable organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic dicarboxylic esters and in particular carbon fibers.
  • the inorganic and organic fillers may be used singly or as mixtures.
  • fillers are used as (e) auxiliaries.
  • fillers are preferably used talc, kaolin, calcium carbonate, barite, glass fibers and / or glass microspheres.
  • the size of the particles of the fillers is preferably to be chosen so that the introduction of the components for the preparation of (ii) in the space between (i) and (iii) is not hindered.
  • the fillers have particle sizes of ⁇ 0.5 mm on.
  • the fillers are preferably used in admixture with the polyol component in the reaction for the preparation of the polyisocyanate polyaddition products.
  • the fillers can be used to reduce the compared to steel, for example, larger thermal expansion coefficient of the polyisocyanate polyaddition products and thus to adapt to the steel. This is particularly advantageous for a permanently strong bond between the layers (i), (ii) and (iii), as this results in lower stresses between the layers under thermal stress.
  • foam stabilizers which are commercially available and generally known to the person skilled in the art, for example generally known polysiloxane-polyoxyalkylene block copolymers, e.g. Tegostab 2219 from Goldschmidt.
  • the proportion of these foam stabilizers in the preparation of (ii) is preferably 0.001 to 10 wt .-%, particularly preferably 0.01 to 10 wt .-%, in particular 0.01 to 2 wt .-%, based on the weight of for the preparation of (ii) used components (b), (e) and optionally (d).
  • the use of these foam stabilizers causes component (c) in the reaction mixture to be stabilized to produce (ii).
  • blowing agent (f) generally known blowing agents can be used from polyurethane chemistry, for example physical and / or chemical blowing agents. Such physical blowing agents generally have a boiling point at a pressure of 1 bar of greater (i.e., at higher temperatures than) -50 ° C. Examples of physical blowing agents are e.g.
  • Suitable chemical blowing agents ie blowing agents which form gaseous products due to a reaction, for example with isocyanate groups
  • blowing agent (f) Preference is given to using water and / or carbamates as blowing agent (f).
  • the blowing agents (f) are used in an amount sufficient to obtain the preferred density of (ii) from 350 to 1200 kg / m 3 .
  • the propellants (f) are particularly preferably used in an amount of from 0.05 to 10% by weight, in particular from 0.1 to 5% by weight, based in each case on the total weight of the polyisocyanate polyaddition products.
  • the weight of (ii) is by definition the same as the weight of the components (a), (b) used and (c), (d), (e) and / or (f) used to prepare (ii).
  • the isocyanates and the isocyanate-reactive compounds are reacted in amounts such that the equivalence ratio of NCO groups of the isocyanates (a) to the sum of the reactive hydrogen atoms of the isocyanate-reactive compounds (b) and optionally (f) 0.85 to 1.25: 1, preferably 0.95 to 1.15: 1 and in particular 1 to 1.05: 1. If (ii) contain at least partially bound isocyanurate groups, a ratio of NCO groups to the sum of the reactive hydrogen atoms of from 1.5 to 60: 1, preferably 1.5 to 8: 1, is usually used.
  • the polyisocyanate polyaddition products are usually prepared by the one-shot process or by the prepolymer process, for example by means of the high-pressure or low-pressure technique.
  • Component (c) may be supplied to the reaction mixture comprising (a), (b) and optionally (f), (d) and / or (e), and / or the individual components (a), (b) already described. , (A) and / or (B).
  • the component that is mixed with (c) is usually liquid.
  • the components are preferably mixed into component (b).
  • the mixing of the corresponding component with (c) can be carried out by generally known methods.
  • (c) can be compressed by generally known loading devices, for example air-charging devices, preferably under pressure, for example from a pressure vessel or by a compressor, eg be supplied through a nozzle of the corresponding component.
  • loading devices for example air-charging devices, preferably under pressure, for example from a pressure vessel or by a compressor, eg be supplied through a nozzle of the corresponding component.
  • the content of (c) in the reaction mixture for the preparation of (ii) can be determined in the return line of the high-pressure machine with well-known measuring devices on the density of the reaction mixture.
  • the content of (c) in the reaction mixture may preferably be regulated automatically on the basis of this density via a control unit.
  • the component density can be determined and regulated online during the usual circulation of material in the machine, even at very low circulation rates.
  • the composite elements obtainable according to the invention find use, above all, in areas in which construction elements are required which withstand great forces, for example as structural parts in shipbuilding, e.g. in ship hulls, for example, double hulls with an outer and an inner wall, and cargo space covers, cargo space partitions, tailboards or in buildings, such as bridges or as construction elements in the house, especially in high-rise buildings.
  • the composite elements according to the invention are not to be confused with classic sandwich elements which contain a polyurethane and / or polyisocyanurate foam as the core and are usually used for thermal insulation. Such known sandwich elements would not be suitable for the aforementioned applications due to their relatively lower mechanical strength.
  • the composite elements according to the invention preferably have a width of 0.2 m to 5 m, preferably 0.5 to 3 m, and a length of 0.5 m to 10 m, preferably 1 m to 5 m.

Landscapes

  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Metal-Oxide And Bipolar Metal-Oxide Semiconductor Integrated Circuits (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cephalosporin Compounds (AREA)

Claims (5)

  1. Procédé de fabrication d'éléments composites présentant la structure en couches suivante :
    (i) 2 à 20 mm de métal, de matière synthétique ou de bois,
    (ii) 10 à 300 mm de matière synthétique,
    (iii) 2 à 20 mm de métal, de matière synthétique ou de bois,
    des corps creux étant présents dans la couche (ii), qui présentent un diamètre extérieur inférieur à 5 mm, caractérisé en ce que, pour la fabrication de (ii), on fait réagir (a) des isocyanates et (b) des composés réactifs par rapport aux isocyanates en présence de corps creux et on ajoute les corps creux au composant (b) et/ou au composant (a) et/ou aux produits liquides de la réaction de (a) et (b).
  2. Procédé selon la revendication 1, caractérisé en ce que les corps creux présentent une densité inférieure à 1 g/cm3.
  3. Procédé selon la revendication 1, caractérisé en ce que les corps creux possèdent une épaisseur de paroi moyenne de 5 à 20 % du diamètre des corps creux.
  4. Procédé selon la revendication 1, caractérisé en ce que les corps creux sont à base de verre, de silicate d'aluminium ou de céramique.
  5. Procédé selon la revendication 1, caractérisé en ce que les corps creux prennent de 1 à 60 % du volume total de la couche (ii).
EP03720337A 2002-03-26 2003-03-19 Procede de fabrication d'elements composites Expired - Lifetime EP1490216B1 (fr)

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DE10213753A DE10213753A1 (de) 2002-03-26 2002-03-26 Verbundelemente
DE10213753 2002-03-26
PCT/EP2003/002844 WO2003080330A1 (fr) 2002-03-26 2003-03-19 Elements composites

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EP1490216B1 true EP1490216B1 (fr) 2008-04-02

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US20120139151A1 (en) * 2010-12-02 2012-06-07 Chen Yu-Ying Additive type bio-decomposable composite preparation method

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WO2003080330A1 (fr) 2003-10-02
JP4702732B2 (ja) 2011-06-15
DK1490216T3 (da) 2008-06-30
AU2003223968A1 (en) 2003-10-08
KR20040096664A (ko) 2004-11-16
US20050161850A1 (en) 2005-07-28
ES2300571T3 (es) 2008-06-16
CN100393508C (zh) 2008-06-11
CA2480036A1 (fr) 2003-10-02
CA2480036C (fr) 2011-02-22
EP1490216A1 (fr) 2004-12-29
DE50309533D1 (de) 2008-05-15
ATE391009T1 (de) 2008-04-15
CN1642735A (zh) 2005-07-20
DE10213753A1 (de) 2003-10-16

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